UNIT – II: QUANTUM DYNAMICS
• Time Evolution Operator and its
Properties
• Schrodinger Equation For The Time
Evolution Operator - Energy
Eigenkets
• Time Dependence Of Expectation
Values
• Time Energy Uncertainty Relation
• Schrodinger Picture And Heisenberg
Picture
• Behaviour of Statekets and
Observables in Schrodinger Picture
and Heisenberg Picture
• Heisenberg Equation of Motion
• Ehrenfest’s Theorem
• Time Evolution of Basekets -
Transition Amplitude
• Energy Eigenket and Eigen Values
of Simple Harmonic Oscillator
Using Creation and Annihilation
Operators
 Time Evolution of Physical System
In CM, the dynamical state of a physical system is defined by
the values of a set of dynamical variables such as position
coordinates and the velocities.

Therefore, the equations of motion, which describe the

evolution of physical system in time are, differential equations
in these variables. For e.g.,

Newton's equations of motion:

Lagrange's equations of motion: .

• Thus evolution of motion is an expression of the functional

dependence of the dynamical variable upon t. Thus, time t is not

an observable but it is a parameter.

Observable
• In physics, an observable is a dynamic variable that can be

measured e.g., position and momentum.

• In CM, it is a real-valued function of all possible system states.

• In Quantum physics, it is an operator, or gauge, where the

property of the system state can be determined by some

sequence of physical operations.

 Time Evolution of Physical System
• In QM,
• time t is treated as a parameter.
• the state of a physical system is represented by a ket in
the Hilbert space.

• Therefore, the equation of motion for a quantum mechanical

system could be a differential equation for the state ket.

• But in QM, the observable quantities are not the state kets, but
the expectation values of a set of Hermitian operators
corresponding to the dynamical variables.

• Therefore in QM, the equations of motion should involve these

expectation values.
 In this chapter, we deal with:

• Change of Physical Systems with time

• Dynamic development of Statekets and/or Observables

or, in other words;

Quantum Mechanical Analogue of Newton’s (or

Lagrange’s or Hamilton’s) Equations of Motion

In QM, Time is just a parameter, not an Operator (Observable)

Time Evolution of Physical System
• In quantum mechanics, the state of a physical
system is represented in an abstract Hilbert
space by the state ket.

• How does a State ket change with time?????

 Time Evolution Operator,
Suppose we have a physical system whose state ket at t0 is |α> .

At later times, the state ket is denoted by |α, t0; t> , where t > t0 .

Since time is a continuous parameter we expect limit t → t0 ,

lim | α, t0; t > = | α, t0> = |α>
𝑡→t0

Time Evolution
| α, t0> = |α> →→→→→ | α, t0 ; t >

These two state kets are connected by an operator called Time

Evolution Operator,

|α, t0> = |α, t0 ; t > .

 Properties of Time Evolution Operator,
1. Unitary requirement for (t, t0) which follows from probability
conservation.

If (t, t0) is taken to be unitary then, †

2. Composition property:
=

• If we consider an Infinitesimal Time Evolution Operator,

, then it must reduce to unity as goes to .
lim =1
𝑑𝑡→0

i.e α ; = α
• Then the form of TEO can be; , where
Ω is a Hermitian operator.
 Properties of Time Evolution Operator,
α α

• Difference between TEO and unity:

where Ω is a Hermitian operator, i.e., Ω† = Ω. Therefore:

† ≈

• The infinitesimal time evolution operator also satisfies the

Composition property:
=
 Properties of Time Evolution Operator, (t, t0)

• = , then it is clear that the operator Ω has

the dimension of frequency or inverse time.

• From Plank-Einstein relation, E = ħ ω. Hence, ω = E/ ħ.

• According to Classical Mechanics, Hamiltonian is the Generator

of Time Evolution. Therefore we can write: Ω = H/ ħ.

• Hence the infinitesimal time evolution operator can be written

as:
𝐻
ħ
Schrödinger Equation for Time Evolution Operator
To get Sch. Equ. or the fundamental differential equation for time
evolution operator, , use the Composition Property:

Which can be written in differential equation form

Formal Solutions to SE for the Time Evolution Operator

• Case 1: Hamiltonian operator is independent of Time (we

deal with this case only – practical interest in elementary
applications)
 iH (t  t0 ) 
U (t , t0 )  exp  
  
• Case 2: Hamiltonian operator is time-dependent but H’s at
different Times COMMUTE
 i t 
U (t , t0 )  exp     dt ' H (t ' )
    t0 
• Case 3: Hamiltonian operator is time-dependent but H’s at
different Times DO NOT COMMUTE (Dyson Series)
 i 
 n

U (t , t0 )  1    
t1 t2 tn

n 1   

t0
dt1  dt2 ....... dtn H (t1 ) H (t 2 )......H (t n ).
t0 t0
 Schrödinger Equation for a Stateket
Schrödinger Equation for time evolution operator:

Multiply both sides of above equation with stateket |α , t0>:

|α , t0> doesn’t depend on t. The above equ. can be re-written as:


i  , t 0 ; t  H  , t 0 ; t
t
 State Ket
Suppose at t = t0, the state ket |α,t=t0> is
expanded in terms of base kets |ai> of some
observable Â

At some later instant of time (t > t0)

The modulus of the individual expansion

coefficient need not be same,
The normalized state ket,

for t > t0,

The normalized state ket,

.

Hence,

It means that if the state ket is initially normalized to unity,

it must remain normalized to unity at all later times.
Since

ˆ  iH (t  t0 ) 
U (t0  dt , t0 )  exp  
  
 Energy Eigenkets
How time evolution operator acts on basekets???
• Basekets are eigenkets of an observable A, such that [A,H]=0,
then eigenkets of A are also eigenkets of H called Energy Eigenkets
whose eigen values are denoted by Ea : H |a> = Ea |a>

• Expand the time evolution operator in terms of projection operator

|a> <a| (= unity).
  iHt    iHt 
exp    a' ' a' ' exp  a' a'
   a ' a ''   
  iHt    iEa 't 
• Taking t0 = 0 we obtain, exp  
 a ' exp   a'
   a'   

• Time evolution operator written in this form enables us to solve

any initial value problem if know the expansion of initial ket in
terms of {|a> }.
• The initial ket expansion is:  , t 0  0   a ' a '    ca ' a ' .
a' a'

• Then we have:
  iHt    iEa 't 
 , t0  0; t  exp   , t0  0   a' a'  exp 
   a'   
• The expansion coefficient changes with time whereas modulus
unchanged as:   iEa 't 
ca ' (t  0)  ca ' (t )  ca ' (t  0) exp 
  
• If the initial state is { a' } then we have
  iEa 't 
initially  , t0  0  a' and at a later time  , t0  0; t  a' exp .
  

• So, if the system is initially a simultaneous eigenket of A and H, it

remains so at all times. The most that can happen is the phase
modulation. It is in this sense that an observable compatible
with H i.e, [A,H]=0 is a constant of motion.
 Time dependence of Expectation Values
How an expectation value of an observable changes as
a function of time?
• At t=0 the initial state is one of the eigenstates of an
observable A that commutes with H is:

At a later time:
• Now the expectation value of some other observable B which
need not commute with  nor with H. For the state ket, <B> is
given by   
B  a i Uˆ  (t ,0) .B. Uˆ (t ,0) a i 
 iEa i t    iEa i t  i
 a exp
  
i
 B exp
 
 a
    
 ai B ai Which is independent of time.
• This implies that the expectation value of an observable
taken with respect to an energy eigenstate does not
change with time.

• That is why an energy eigenstates are called

STATIONARY STATES.
If the expectation value is taken with respect to a
superposition of energy eigen states:
• Initially an eigenket |α,t0 = 0> be represented as:

 , t0  0   a i  a i   ca (t0  0) a ii
i i

 , t0  0; t  Uˆ (t )  , t0  0  Uˆ (t ) ca (t0  0) a i
i
i

 , t0  0; t   ca i (t0  0)U (t ) a
ˆ i

i
 , t0  0; t   ca i (t0  0) exp[ Ht ] a i

i 
i
 , t0  0; t   ca i (t0  0) exp[ Ea i t ] a i
i 
If the expectation value is taken with respect to a
superposition of energy eigen states:

So in the case of NONSTATIONARY STATE, the expectation

value consists of oscillating terms whose angular frequencies are
determined by Bohr frequency condition.
 Correlation Amplitude
• This section deals with how state kets at different times are
correlated with each other.
• Suppose the initial ket at t=0 be given by and at a later
time it is .
• We are concerned with the extent to which the state ket at a
latter time t is similar to the state ket at t=0. We therefore
construct their inner product:

• C(t) is known as the correlation amplitude. The modulus of

C(t) provides a quantitative measure of the “resemblance’’
between the state kets at different times.
 Schrödinger Picture V/S Heisenberg Picture
• Unitary operators : We have where U may stand for
T(dx) or is the stateket corresponding to a physical system
that actually has undergone translation or time evolution.
– Unitary transformations changes the stateket, but the inner product remains
unchanged.

• Some transformations does not affect the stateket but the operator.
i.e, (using associative axiom of multiplication)

This mathematical identity suggests 2 approaches to unitary

transformations:
• Approach 1 : The SchrÖdinger Picture - with
operators & observables are unchanged but the stateket vary
with time.
• Approach 2 : The Heisenberg picture - X → with
statekets unchanged but observables and operators vary with
time.
 Statekets and observables in SP and HP :

• In the SP the operators corresponding to observables like X are

fixed in time while statekets vary with time.

• In HP the operators corresponding to observables vary with

time, the statekets are fixed at what they were at to.

• It is convenient to write:

• In SP, at t=0, these observables coincide, but the time

evolution operator that affects statekets.
• The statekets in two pictures also coincide at t=0;

• at later time the HP stateket is frozen to what it was at t=0.

i.e., , independent of time.

• But the SP stateket is .

• The expectation value <A> is the same in both pictures.

--------------------- (1)
 Heisenberg Equation of motion
• Assuming that the operator, does not depend explicitly on
time, we obtain (by differentiating the eqn (1))

A H  U  A SU
A H U  S  S U
 A U U A
t t t
• By the Schrödinger eqn we have, U (t , t0 )
i  HU (t , t0 )
t
U 1
 HU
t i

U 1 
 U H
t i
 Heisenberg Equation of motion
A H U  S  S U
 A U U A
t t t
A H 1   S 1
 U HA U  U A
S
HU
t i i
A H
t

1
i
  U  HUU  ASU  U  ASUU  HU 
A H
t

1
i
  U  HUAH  A H U  HU 
A H
t

i

1 H 
A , U HU  
1 H
i
A ,H 
Heisenberg equation of motion →

If = 0, then it is a constant of motion.

 Some Features of Quantum Mechanical Evolution
Free Particles; Ehrenfest’s Theorem - An interesting application of
the use of the equations of motion for the mean value of an
observable. Consider the motion of a particle under the influence
of a force derivable from a scalar potential.
  
F ( R)  V ( R)
Quantum mechanically, this corresponds to the Hamiltonian:

Let us now consider how the mean values & and29

associated with the corresponding quantum mechanical
observables change in time.
 Some Features of Quantum Mechanical Evolution
Ehrenfest’s Theorem - First, we examine the equation of motion for
the position operator , which being independent of time
leads to the equation of motion

d  R (t ) 1  
  R , H 
dt i  

d  R (t ) 1  1  2  
 R , P  R , V
dt i 
 2m

 
   



Since V is a function of R, the second commutator vanishes.

The 𝑥 component of the first commutator is
R, P   R, P  R, P  R, P   R, P 
2
x
2
y
2
z
2
x
2 30

R, P   P R, P   R, P P  2iP

x
2
x x x x x
Put back this into the equation of motion for 〈R(t)〉 to obtain:

Therefore,

d  R (t ) 1   1 1  2
  R , H   R , P
dt i   i 2 m 
 


 P
d  R (t ) 1 1 
 2i P 
dt i 2 m m

31

which, brackets aside, looks like its classical counterpart (v=p/m).

Thus, as in classical mechanics the mean velocity equals
the mean momentum divided by the mass.
In a similar fashion we can compute the equation of
motion for the mean momentum,

d  P (t ) 1   1  1  2  
 P, H   P, P    P, V  
dt 
i   i 
 2m

   

Here the kinetic energy term disappears, but the

potential energy term does not, since it is a function of32
the operator 𝑹, which does not commute with 𝑷.
Thus, we make the identification    

 P , V   i F ( R )
 
where is clearly the force operator.
Using this result in the equation of motion we find that

d  P (t ) 1   1   
  P, V   i F ( R )   F 
dt i   i
Thus, the equations of motion for the position and momentum
operators can be written as:
 
d 2  R d  P 
m 2
  F
dt dt
33
which looks like Newton's equations, aside from the taking of
expectation values. This is known as Ehrenfest Theorem.
Ehrenfest’s Theorem
These classically familiar-looking (resembling) expressions
are referred to as Ehrenfest's equations of motion for the
mean values of position and momentum.

34
 SIMPLE HARMONIC OSCILLATOR PROBLEM
One of the most important problems in QM.
It is used to illustrate the basic concepts and methods in QM.
It has applications in Molecular Spectroscopy, Solid State physics,
Quantum field Theory etc.

ENERGY EIGENKETS AND ENERGY EIGENVALUES

p2 m 2 x 2
H  
The basic Hamiltonian for SHO is 2m 2 where
ω is the angular frequency with  .
k/m
35
Now we define two non-Hermitian operators,

m  ip 
a x 
2  m 
m  ip 
a †
x 
2  m 
known as annihilation operator and creation operator.

Using the canonical commutation relations, we get:

 1 
[ a, a ]   [ x, p ]  [ p, x]  1
†

 2i  36
Define the Number Operator (Hermitian) N  a a
†

 m 
 2 p 2
  i 
a a  x  2 2   
†
[ x, p ]
 2  m    2 
 1  m  2 2
x m  p 2
  i 
a † a        i
 
 2 2 m 2
 2
  2 
H 1
a a
†

 2
 1
The relation between the number operator H    N  
and the Hamiltonian operator is:  2

Energy Eigen value equation for the number operator N:

N n nn
37
  1
Thus we have H n   n   n
 2

which means that the energy eigenvalues are given by

 1
En   n  
 2

Physical Significance of a, a† and N

[ N , a ]  [a a, a]  a [a, a]  [a , a]a  a
† † †

[a, a ]  1
†

Similarly we can derive [ N , a † ]  a †

38
 [N, a ]  a
† †

 Na † n  ([ N , a † ]  a † N ) n
Na † n  ( Na †  a † N  a † N ) n
Na † n  ( n  1) a † n
Similarly we can write:
Na n  ([ N , a ]  aN ) n
Na n  ( n  1) a n
These relations imply that a n and a n  are also eigenkets of N
†

with eigen-value increased (decreased) by one. Because the increase

(decrease) of n by one amounts to the creation (annihilation) of one
quantum unit of energy ħω, the creation operator (annihilation
operator ) for a†(a) is believed appropriate. 39
The equation Na n  n  1a n implies that a n and n  1
are the same up to a multiplicative constant. i.e.,
a n  c n 1
where c is a constant which can be determine by normalizing both n
and n  1 .
na an  c n 1 n 1  c
† 2 2

We have a†a  N
 n | c 2 |
c  n
a n  n n 1
Similarly we can derive, a n  n 1 n 1
†
40
 a n  n n 1
a n  n 1 n 1
†

Suppose we keep on applying the annihilation operator a to both

sides of above equation:

a n  n n 1
a2 n  n( n  1) n  2
a3 n  n( n  1)(n  2) n  3
We can obtain numerical operator eigenkets with smaller values of
n until the sequence terminates, which will happen if we start
41
with a positive integer n.
It is also a requirement that n  n N n 0 which implies
that n can never be negative.

So we conclude that the sequence must terminate with n=0 and that
the allowed values of n are nonnegative integers.

Thus the smallest possible value of n=0, the ground state of harmonic
oscillator has 1
E0  
2
Successively apply the creation operator to the ground state:
.
1  a† 0
.
 a†   a†2 
2  1   0 .
 2 
 2 
 a†n 
 a†   a †3  n    0
3   2   0  n! 
 3   
 3!  
42
It is also a requirement that n  n N n 0 which implies
that n can never be negative.

So we conclude that the sequence must terminate with n=0 and that
the allowed values of n are nonnegative integers.

Thus the smallest possible value of n=0, the ground state of harmonic
oscillator has 1
E0  
2
Successively apply the creation operator to the ground state:
.
1  a† 0
.
 a†   a†2 
2  1   0 .
 2 
 2 
 a†n 
 a†   a †3  n    0
3   2   0  n! 
 3   
 3!  
43
 Define operators
i  1
a  ( P  i x) a  ( P  i x)
2 i 2
 
a a a is the complex conjugate (adjoint) of a since P and x are Hermitian.

Then
 1
a a  [( P  i x )( P  i x )]
2
1 2
 [ P  i xP  i P x  x ]
2

2
1 2
 [ P  i ( xP  P x )  x ]
2

2
1 2 i
 [ P  x ]  [ x, P ]
2

2 2
Hamiltonian commutator
 1
 aa  H  1
2
Copyright – Michael D. Fayer, 2007
  1
aa  H  1
Similarly 2
 1 2
a a  [ P  i ( xP  P x )  x ]
2

2
 1
a aH 1
Therefore 2
1  
H  (a a  a a ) Very different looking from Schrödinger Hamiltonian.
2
and
a, a    1
 
Can also show

 
[a , H ]  a [a , H ]   a

Copyright – Michael D. Fayer, 2007

Now consider
H  a E   ( E  1)  a E 
aH E  Ea E eigenket of H
commutator these are same
a, H   a H  H a  a rearrange Operate H on ket, get same ket back
times number.
aH  Haa
 a E  is eigenket with
Then, eigenvalue, E - 1.

( H a  a) E  a H E  E a E H  a E   ( E  1)  a E 

eigenvalue eigenket
Ha E  a E  E a E transpose
a E  E 1

Ha E  E a E  a E factor Maybe number multiplying.

Direction defines state, not length.
Copyright – Michael D. Fayer, 2007
 a is a lowering operator. H  a E   ( E  1)  a E 
It gives a new eigenvector of H with one unit lower energy.

a E  E 1
a E  E 2
2 Each application gives new ket one with one unit
lower energy.
a E  E 3
3

Could keep doing this indefinitely, For eigenvector E0

but 1
E
2  1
Therefore, at some point we have a value of a  a E0   ( H  1) E0
2
E, call it E0, 1
such that if we subtract 1 from it  ( E0  ) E0  0
2
1
E0  1  E0 
1
2 not zero
2
But E0 - 1 can't be < 1/2. Therefore a E0  0 1 in conventional
E0  h units
2 Copyright – Michael D. Fayer, 2007
Raising Operator
 
a  H E   E a E

  
a  H E   ( H a  a ) E using the commutator

rearranging, operating, and factoring as before

H  a E   ( E  1)  a E 
 

These are the same.

Therefore,  a  E  is an eigenket of H with eigenvalue E + 1.

 


number, but direction defines state
a E  E 1


a takes state into new state, one unit higher in energy.
It is a raising operator.

Copyright – Michael D. Fayer, 2007

E0 is the state of lowest energy with eigenvalue (energy) 1/2.
Apply raising operator repeatedly. Each application gives state
higher in energy by one unit.
1
H E0  E0 eigenvalue, one unit higher in energy
2
3
H  a E0   E0  1


2
5
H  a E0   E0  2
2

2
7
H  a E0   E0  3
3

1 3 5 7
E , , , ,  1
En   n  
2 2 2 2  2

 1
With normal units En   n   h Same result as with Schrödinger Eq.
 2
Copyright – Michael D. Fayer, 2007
Eigenkets labeled with energy

1
E  n
2
Can relabel kets with quantum number

1
E  n  n Take n to be normalized.
2
Raising and Lowering operators

a n  n n  1 a n  n n  1

n  n  1 n  n numbers multiply ket when raise

or lower


a n  ( n  1) n  1 a n  n n 1

Will derive these below.

Copyright – Michael D. Fayer, 2007
Consider operator

a a operating on n

 
a a n a n n 1
n n
Therefore

a a n n n


n is an eigenket of operator a a with eigenvalue n.


a a number operator. Eigenvalue – quantum number

Important in Quantum Theory of Radiation and Solids


a and a called creation and annihilation operators.
Number operator gives number of photons in radiation field
or number of phonons (quantized vibrations of solids) in crystal.

Copyright – Michael D. Fayer, 2007

Units in the raising and lowering operators
i 1 1/ 2 
a  1/ 2 
P  i k x Many constants. This is the reason
(2  )  m 1/ 2
 why derivation was done in units
such that m  1 k  1 1 .
  1
1 1/ 2 
a   Need constants and units to work
i (2  )1/ 2  m1/ 2
P i k x
 problems.

 aa

 
2
1

1/ 2  2k 1/ 2
x  Add operators, P cancels.

1/ 2
 2k 
  x
 

 
1/ 2

x 
 2 k 

 aa

 x in terms of raising and lowering operators.

 m 
1/ 2

P  i 
 2 
 a  a  
Subtract operators, get P in terms of
raising and lowering operators.
Copyright – Michael D. Fayer, 2007